Abstract
Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1,2,3,4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620–650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m−2.
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Data availability
The data that support the findings of this study are available at the University of Cambridge repository (https://doi.org/10.17863/CAM.108810).
Change history
25 June 2024
A Correction to this paper has been published: https://doi.org/10.1038/s41586-024-07736-y
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Acknowledgements
This work is financially supported by the National Key Research and Development Program of China (Grant Nos. 2022YFE0200200 and 2022YFB3602900). We acknowledge financial support from the National Natural Science Foundation of China (Grant Nos. 62174104, 62321166653 and 51972137), the Program of Shanghai Academic/Technology Research Leader (Grant No. 22XD1421200), the Shanghai Natural Science Foundation (Grant No. 23ZR1423300), the Shuguang Program of Shanghai Education Development Foundation and Shanghai Municipal Education Commission (Grant No. 22SG40), the Innovative Capacity Building Foundation of Jilin Province Development and Reform Commission (Grant No. 2023C034-5) and the Science and Technology Planning Project of Jilin Province (Grant No. 20230101020JC). K.J. acknowledges a Royal Society studentship. L.D. acknowledges funding support from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (ERC fundings: PEROVSCI, 957513 & HYPERION, 756962) and UKRI Horizon Europe Guarantee MSCA Marie Skłodowska-Curie Postdoctoral Fellowship (grant nos. EP/Y029429/1). S.D.S. thanks the Royal Society and the Tata Group (Grant No. UF150033) and funding from European Research Council (HYPERION, Grant No. 756962) and the Engineering and Physical Sciences Research Council (Grant Nos. EP/R023980/1 and EP/V027131/1). We thank the staff of the BL17B1, BL02U2, and BL19U2 beamlines at SSRF for providing the beam time, the User Experiment Assist System at SSRF for their help and the Supercomputing Center of the University of Science and Technology of China for simulations. We thank L. Zhang at Jilin University for providing the partial computational resource during the manuscript revision process, G. Xie at Xiamen University for angle-dependent photoluminescence measurements and Q. Lin at Wuhan University for optical constant measurements.
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X.Y. and N.W. conceived the idea and guided the work. L.K. and Y.W. fabricated and tested the LEDs. Y.S. performed the electroluminescence kinetics measurements and analysed the data under N.C.G.’s guidance. K.J. performed the hyperspectral imaging measurements with S.D.S.’s guidance. L.D. and S.M. performed the transient absorption characterization and analysed the data under the guidance of S.D.S. and R.H.F. Y.Y. carried out the in situ GIWAXS measurements and directed the data analysis. B.Z., Y.L. and Z.L. carried out the theoretical calculations. W.L. and C.C. carried out optical simulations. J.D. performed the NMR, Kelvin probe force microscopy, excitation-intensity-dependent PLQYs and temperature-dependent photoluminescence measurements. J.F. helped fabricate the perovskite films and collect the data. L.K. wrote the manuscript, which was revised by N.C.G., N.W. and X.Y. All authors discussed the results and commented on the paper.
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Extended data figures and tables
Extended Data Fig. 1 DOS analysis.
Electronic DOS curves for CsPbI3 with different atomic numbers. The reduction in perovskite dimensionality is simulated by decreasing the number of atoms. As the dimensionality of CsPbI3 decreases, the antibonding states are pushed to lower energies, and the bonding states just below the Fermi level are, conversely, pushed to higher levels, suggesting a weakened hybridization and bonding.
Extended Data Fig. 2 Optical characterization of perovskite thin films.
a-d, PL spectra of perovskite thin films with different amounts of MOPA (a), MBA (b), MPPA (c) and mixed MBA and MPPA (d) ligands. The Pb concentration is fixed at 0.12 M. e, PL spectra of MM-MOPA perovskite films with different amounts of MOPA (the molar concentrations of MOPA are from 0.01 − 0.05 M, with Pb, MBA and MPPA concentrations fixed at 0.12 M, 0.06 M, and 0.06 M, respectively). f, Time-resolved PL spectra of perovskite films with MBA, MPPA, and MOPA, respectively.
Extended Data Fig. 3 XPS, FTIR, and NMR studies.
a,b, XPS spectra of Pb 4 f (a) and O 1 s (b) for the perovskites without and with MOPA. The Pb 4 f peaks in MOPA-perovskite were shifted towards lower binding energies, while the O 1 s peak of methoxy group was shifted to a higher binding energy compared with MOPA. This is caused by the interaction between perovskite and methoxy group of MOPA. c, FTIR spectra of the MOPA molecule and MOPA-perovskite. The C-O stretching vibration peaks of the MOPA are shifted to lower wavenumbers when the methoxy group of MOPA interacts with perovskite. d, Solid-state 207Pb NMR spectra for the perovskites without and with MOPA. The 207Pb NMR signal of the perovskite centered at 1,560 ppm was shifted to 1,657 ppm upon incorporating MOPA.
Extended Data Fig. 4 In situ GIWAXS characterization of perovskite thin films.
a,b, Integrated one-dimensional GIWAXS spectra (a) and zoomed-in region (b) of the MM-MOPA perovskite films. The signals are assigned by analysing the diffraction peaks of the corresponding X-ray diffraction patterns (Supplementary Fig. 7).
Extended Data Fig. 5 Photophysical characterization of perovskite thin films.
a,b, Two-dimensional map of temperature-dependent PL spectra of M-MPPA (a) and MM-MOPA (b) perovskite films. c,d, The fitted curves of the integrated PL intensity as a function of 1/T for M-MPPA (c) and MM-MOPA (d) perovskite films.
Extended Data Fig. 6 Stability characterization of perovskite thin films.
a,b, Time-dependent PL intensity measurements for the M-MPPA and MM-MOPA perovskite films in ambient air (35% humidity, 25 °C) for 60 min (a) and under 365 nm UV irradiation (b).
Extended Data Fig. 7 Device performance of PeLEDs.
Electroluminescence (EL) spectra a,d, J-V-L b,e, and corresponding EQE-J c,f, curves for the MM-MOPA based PeLEDs emitting at 627 nm (a-c) and 645 nm (d-f), respectively.
Extended Data Fig. 8 Operational lifetime of PeLEDs.
a,b, Half-lifetime (T50) measurements for MM-MOPA based PeLEDs emitting at 627 nm (a) and 638 nm (b), respectively.
Extended Data Fig. 9 Nanoscale EL heterogeneity of PeLEDs.
a-f, Hyperspectral EL images of M-MPPA (a) and MM-MOPA (d) based PeLEDs at an operating voltage of 6 V. Hyperspectral EL intensity images of M-MPPA (b,c) and MM-MOPA (e,f) based PeLEDs at operating voltages of 6 V (b,e) and 8 V (c,f). EL signals were collected from 550 to 750 nm. Scale bar, 10 µm.
Supplementary information
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Kong, L., Sun, Y., Zhao, B. et al. Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure. Nature 631, 73–79 (2024). https://doi.org/10.1038/s41586-024-07531-9
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DOI: https://doi.org/10.1038/s41586-024-07531-9
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